NOTES

C H E M I S T R Y

ATOMIC STRUCTURE
HYDROGEN SPECTRUM DEMYSTIFIED

What you already know What you will learn

• Energy level diagram • Spectroscopy

• Ground state • Emission and absorption spectrum
• Ionisation energy • Energy level of hydrogen atom
• Ionisation potential • Rydberg Formula
• Spectral series in hydrogen atom

BOARDS
Spectroscopy

The branch of science that deals with the study of spectra

• An instrument that is used to separate the radiations of different wavelengths is known as a
spectrograph or a spectroscope. For example, a prism is the simplest spectrograph.
• When incident radiation passes through the spectroscope, the radiation splits in its fundamental
wavelengths. For example, a prism disperses the sunlight into seven colours (VIBGYOR).
• The pattern obtained after passing radiations through the spectroscope is known as a spectrogram
or a spectrum. When sunlight is passed through the prism, it splits into different wavelengths.
When it is collected in a systematic way it is known as a spectrogram of sunlight.
• Infrared and ultraviolet (UV) rays can also be part of the spectrum that are not visible to human
eyes.

Prism Screen

White Light

Spectrum

Fig. 1: Splitting of light using the prism as a spectroscope

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 02

BOARDS
Classification of Spectra

Emission
spectrum
Spectra based on
origin
Absorption
spectrum

• The spectrum produced by the radiation emitted by a

substance due to the de-excitation of electrons in atoms
is known as emission spectrum.
• When the spectrum of electromagnetic radiation is passed
through a sample (solution or gases), certain wavelengths
are absorbed by the sample that are used to excite the
electrons to higher energy levels. When we obtain the
spectrum of the remaining radiation, we observe dark lines
corresponding to the wavelengths that are missing from Fig. 2: Emission spectrum
the spectrum. This is known as absorption spectrum. and Absorption spectrum
In the given figure, the absorption spectrum of a sample (gas or solution) has been shown, in
which certain wavelengths are absorbed that results in dark lines.

BOARDS NEET
Emission Spectrum

• Emission spectrum is the spectrum of radiation emitted by a substance.

Continuous

Emission spectrum
on the basis of nature

Discrete

Continuous Spectrum

• Continuous spectrum is continuous distribution of colours (VIBGYOR) such that each colour
merges into the next one. VIBGYOR
In the figure, a continuous spectrum of sunlight has
been shown that consists of violet, indigo, blue, green,
yellow, orange, and red colours (VIBGYOR). When we
move from the violet colour to the red colour, we find
that the wavelength increases and energy decreases. Fig. 3: Continuous spectrum of light
• Each wavelength of colour is merging such that there is no dark line or space in between them,
making it a continuous spectrum. For example, sunlight or the light of a bulb splitted by the prism,
which is known as the solar spectrum or the bulb-light spectrum. It is an emission spectrum and
a continuous spectrum.

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 03

Discrete Spectrum

A physical quantity is said to be discrete if it takes only distinct values with gaps between one value
and the next. Discontinuous or discrete spectra consists of only some wavelengths of light, unlike
the spectra of white light.

Line spectrum

Discrete spectrum

Band spectrum

Line spectrum

• This is an ordered arrangement of lines of

particular wavelengths separated by dark
spaces.

Fig. 4: Line spectrum

There are several lines of certain wavelengths that indicate that only photons of few wavelengths
are emitted when an electron is de-excited to lower energy level, resulting in line spectrum.
• Generally, the spectra of atoms, like the hydrogen atom, consists of sharp and well-defined lines
corresponding to definite frequencies known as the line spectra.
• Line spectrum of each element is unique like our fingerprints. Hence, it is used in recognising
an unknown element.
• A line spectrum has bright lines over a dark background.

Continuous
spectrum

Sodium

Hydrogen

Calcium

Mercury

4000 Å 5000 Å 6000 Å 7000 Å

Fig. 5: Line spectra of different elements

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 04

Band Spectrum

• When a continuous band is separated by a dark space, it is known as a band spectrum.

Fig. 6: Band spectrum

• There are several photons of nearly the same wavelength emitted that results in the band
spectrum. No photon is emitted corresponding to the wavelength where dark lines are present.
• Generally, molecular spectra consist of sharp and well-defined bands corresponding to the
definite frequencies known as the band spectra.
• Band spectrum consists of bright bands over a dark background.

BOARDS NEET
Absorption Spectrum

• In the absorption spectrum some dark lines are obtained that are separated by coloured bands.
• When electromagnetic radiation passes through the sample, electrons absorb energy and jump
to higher energy states from lower energy states. When a spectrum is obtained, we see that
certain wavelengths are absent from the spectrum that are absorbed by the sample. This is
known as the absorption spectrum.
• The intensity of photons (number of photons falling per unit area per unit time), corresponding
to a particular wavelength that is used in the excitation of electrons to higher energy states,
decreases as they are absorbed by the sample.

Gas in Screen
Ground State Prism

light
source

Fig. 7: Absorption spectrum obtained by the passing of light from a gaseous material

In the fig. 7, electromagnetic radiations are transmitted from the sample present in ground state
and some of the radiations are absorbed by the sample. When the radiation is passed from the
prism, it splits into fundamental wavelengths leaving dark spaces on the screen, corresponding
to the wavelengths that are absorbed by the sample.

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 05

BOARDS
Emission vs Absorption Spectrum

• When an electron absorbs a photon, it is excited to a higher energy level. The spectrum obtained
is known as the absorption spectrum of an electron. Whereas, when the electron releases the
photon and comes to a lower energy level, the spectrum of the emitted radiation is known as
the emission spectrum.
• An absorption spectrum is not identical to the emission spectrum. For example, an electron
absorbs a photon and goes from the first to the fifth orbit. However, it is not necessary that it will
be directly excited to the fifth orbit or emit the photon of equal energy. It can take another path
(example: 5 → 4 → 3 → 2 → 1) to reach the first orbit. Hence, the spectrum we got is not identical
to the emission spectrum.
• When the absorption spectrum is superimposed by the wavelength absorbed, we will get the
continuous spectrum.

Emission
spectrum

Absorption (Emission + Absorption) spectra =

spectrum Continuous spectrum

Fig. 8: Absorption spectrum and absorbed wavelength combines to give continuous spectrum

BOARDS NEET
Emission Spectrum of Hydrogen

• The hydrogen spectrum is discrete because specific wavelengths of light are emitted by a
hydrogen atom when electrons are de-excited to lower energy levels.
• These lines are also known as emission lines or spectral lines.
• The relation between the wavelengths of spectral lines of the hydrogen atom and how the energy
possesed by the electron varies with distance from the nucleus. However, it did not explain the
structure of the atom. Rydberg explained only a mathematical formula to find the wavelength and
the wavenumber.
• Bohr’s theory was able to explain the spectrum of hydrogen atoms by providing energy levels
in hydrogen atoms. However the theory could not explain the further splitting of the hydrogen
spectrum known as the hyperfine spectrum.

BOARDS NEET
Energy Level Diagram for a Hydrogen Atom

• Bohr’s theory explains that in a hydrogen atom, there are fixed energy levels that are denoted
by n = 1, 2, 3...
• The difference between the energy levels can be calculated by Ehigher - Elower.
• For example, the energy difference between the first and the second energy level is 10.2 eV. It
is almost 78% of the ionisation energy of the hydrogen atom.
• When an electron is de-excited, a photon is emitted. These emitted photons are observed in the
hydrogen spectrum.

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 06

n=∞ 0 eV
∆E = 0.544 eV
n=5 -0.544 eV
∆E = 0.306 eV
n=4 -0.85 eV
∆E = 0.66 eV
n=3 -1.51 eV
∆E = 1.89 eV
Energy

n=2 -3.4 eV

∆E = 13.6 eV
∆E = 10.2 eV

n=1 -13.6 eV
Fig. 9: Energy level diagram for a hydrogen atom

BOARDS NEET
Rydberg Formula

Energy of an electron is given by Where

Z  2 RH = 1.09678 × 107 m-1 ≅ 1.1 × 107 m-1
E n1 = E 0  2 
 n1  Value of n (n1 < n2) will be a positive integer.
n1 = 1, 2, 3….
Where E0 is the energy of the 1st orbit in the
hydrogen atom and has a negative value Z is n2 = n1 + 1, n1 + 2....
the atomic number and n1 is the shell number. We can also write
Energy difference between n1 and n2 (n2 > n1) is 1 = ν
given by λ
∆E= En2 − En1 1
= ν is known as the wave number (number of
λ complete wave cycles of an electromagnetic
 1 1 
= ∆E E 0 Z 2  2 − 2  wave that exist in one metre of the linear space)
 n2 n1 
For an atom,
Putting the value of E0 = -2.18 × 10-18 J atom-1
1
 1 1  λ = m
∆E −18 2
= 2 .18 × 10 Z  2 − 2  J atom −1
2  1 1 
RH Z  2 − 2 
 n1 n2   n1 n2 
Also, we know, Substituting the values of all the constants,
hc 1
∆E = = 912 Å
λ RH
1 2 .18 × 10 −18 2  1 1 912
Z  2 − 2  m−1 λ= Å
λ hc  n1 n2  2  1 1
Z  2 − 2
2 .18 × 10 −18  n1 n2 
RH = is a constant value and equal to RH
hc Using this equation we can calculate the
1  1 1 wavelength, the energy, and the frequency of
= RH Z 2  2 − 2  m−1 radiation during the transition of electrons.
λ  n1 n2 
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 07

BOARDS NEET
Spectral Series of the Hydrogen Atom

• The wavelength of the hydrogen spectrum is classified in a series that is known as the spectral
series. During the de-excitation of electrons from higher energy levels to lower energy levels,
an electron can take many pathways. For example, if an electron is in fifth excited state, i.e., the
sixth energy state, then it can de-excite via (6 → 5, 5 → 4, 4 → 1) or (6 → 4, 4 → 2, 2 → 1), etc. On
the basis of the final state to which the electrons de-excite, the line spectra are divided into the
following series:
• Lyman series: It is the ultraviolet emission lines of the hydrogen atom when an electron is
de-excited from any excited state (n > 1) to the ground state (n = 1).
• Balmer series: It is the name given to a series of spectral emission lines of the hydrogen atom
that results when the electron shows transitions from any higher energy level to the energy
level with the principal quantum number 2, i.e., first excited state (n = 2). The first four lines in
the Balmer series correspond to the visible region.
• Paschen series: It is the series of lines in the spectrum of the hydrogen atom that corresponds
to transitions from the higher excited state to the second excited state (n = 3). These spectral
lines correspond to the near infrared (IR) region.
• Brackett series: It is a series of emission lines when an electron jumps down from a higher
energy level to the fourth energy level (n = 4) of the hydrogen atom. These spectral lines
correspond to the infrared (IR) region.
• Pfund series: It is the series of emission lines when electrons jump to the fifth energy level
(n = 5) from higher energy levels. These spectral lines correspond to the far infrared (IR) region.
• Humphrey series: It is the series of emission lines when an electron jumps to the sixth energy
level (n = 6) from higher energy levels. These spectral lines belong to the far infrared (IR) region.
n=∞
n=7
n=6
n=5
n=4
n=3
Paschen Brackett Pfund Humphrey
series series series series
n=2
Balmer
series

n=1
Lyman series
Fig. 10: Spectral series of a hydrogen atom

Note

As we move from the Lyman series to the Humphrey series, the wavelength increases while the
frequency decreases (considering that the electron is de-excited from the same energy levels).

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 08

Lyman Series

• Lyman is the first spectral series and wavelengths corresponding to this series were found to lie
in the UV region by Lyman.
• When electrons move to the first energy level from any other higher energy level in hydrogen
atom it is known as the Lyman series. Hence, n2 can take the values as 2, 3, 4…, and n1 has the
value as 1.
• The wavenumber or wavelength of the emitted radiation in this transition can be calculated using
1  1 1 
=
R H  2 − 2  because for hydrogen atom Z = 1
λ  1 n2 
Where
RH = Rydberg’s constant
n1 = 1 (Final state)
n2 = 2, 3, 4… (Initial state)
• We can also calculate the wavelength of the last line (n2 = ∞) that has the highest energy. The
last line in any spectral series is known as the series limit (n2 = ∞).
1  1 1 1
.e., λ
= R H  2 − 2  i=
λ 1 ∞  RH

• First line is also known as α lines, for α lines n1 = 1 and n2 = 2 and it has energy 10.2 eV. Similarly
second line is known as β lines, for β lines n1 = 1 and n2 = 3.
• Last line of the Lyman series will be ∞ → 1 and it has energy 13.6 eV.
• The range of energy and wavelength of radiations which are emitted corresponding to Lyman
series can be given as:
10 .2 eV ≤ ∆ E Lyman ≤ 13.6 eV
12400 12400
Å ≤ λ Lyman ≤ Å
13.6 10 .2
• For the calculation of the longest wavelength, we need to take the minimum energy difference
and vice-versa.
hc
∆E =
λ
• The first spectral line has the minimum energy difference and the largest wavelength. Whereas,
the last spectral line has the maximum energy difference and the minimum wavelength.

Balmer Series

• When electrons move to the second energy level (n1 = 2) from any other higher energy level in
hydrogen atom (n2 = 3, 4, 5..), it is known as the Balmer series. It is the second spectral series
in the hydrogen atom.
• The first four lines in the Balmer series correspond to the visible region, i.e., four photons
(n2 = 3, 4, 5, 6 to n1 = 2) of the hydrogen atom are in the visible spectrum and can be seen by
human eyes.

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 09

• The wave number ( v ) of the emitted photon in this transition can be calculated using
1  1 1 
ν=
= R H  2 − 2  because for hydrogen atom Z = 1
λ 2 n2 
Where
RH = Rydberg’s constant
n1 = 2 (Final state)
n2 = 3, 4, 5… (Initial state)
• When an electron moves from n2 = ∞ → n1 = 2, it is known as the series limit of the Balmer
series and this line will have the highest energy in the Balmer series under the UV region. The
wavelength of the emitted radiation that corresponds to this transition can be calculated by
1  1 1 4
= RH  2 − 2  = i.e., λ
λ 2 ∞  RH
• When an electron is de-excited from the initial energy state (n1 = 3) to the final state (n2 = 2), it is
known as α line that consists of the red colour.
n=∞
n=6
n=5
n=4
Energy

n=3

n=2 Limiting line

α βγ δ ε
Balmer series
Fig. 11: Balmer spectral lines
In the figure, four spectral lines that lies in the visible spectrum have been shown. In these four
lines, the first line, which is the α line, will be of red colour.

Spectrum characteristic

Line spectra is a characteristic of which of the following species?

(a) Molecules (b) Atoms (c) Radicals (d) None of these

Solution

Each molecule, atom, and radical species have its typical spectrum. The line spectrum is widely
used to identify the atoms as the line spectrum is a characteristic of atoms. Molecules and radicals
also consist of line spectra but they do not have well defined spectra like atoms.
Hence, option (b) is the correct answer.

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 10

Finding the maximum wavelength line

What is the maximum wavelength line in the Lyman series of He+ ion?
1 1
(a) 3RH (b) (c) (d) None of the above
3R H RH

Solution

The spectral line, corresponding to maximum Substituting the value of Z for He+ (Z = 2) and
wavelength in Lyman series, is the first line, i.e., n1 = 1 and n2 = 2
n1 = 1 and n2 = 2
1  1 1 1 3
= R H 22  2 − 2  i.e., = R H 4  
From the Rydberg formula λ 1 2  λ 4
1  1 1  1 1
= R H Z2  2 − 2  = R H × 3 i.e., λ =
λ n
 1 n 2  λ 3R H

Option (b) is the correct answer.

Finding the ratio of the series limit

If RH is Rydberg’s constant for hydrogen atoms, then what is the ratio of series limits for wave
number of the Balmer series of hydrogen and Li2+?
RH 9 RH 1
(a) (b) (c) 9 (d)
9 4 9

Solution

Step 1: Calculating the series limit for wave Step 2: Calculating the series limit for wave
number of the Balmer series for the number of the Balmer series for Li2+
hydrogen atom The spectral line, corresponding to the series
The spectral line, corresponding to the series limit in the Balmer series in Li2+, is the last line,
limit in the Balmer series in H, is the last line, i.e., i.e., n1 = 2 and n2 = ∞
n1 = 2 and n2 = ∞ Using the Rydberg formula
Using the Rydberg formula,
1  1 1
 1 = RH Z 2  2 − 2 
1 1 λ  n1 n2 
= RH Z 2  2 − 2 
λ  n1 n2 
Substituting the value of Z = 3 for Li2+ ion, n1 = 2
Substituting the value of Z = 1 for the hydrogen and n2 = ∞
atom, n1 = 2 and n2 = ∞
1  1 1  9R
= R H 32  2 − 2  = H ......(2)
νLi2+ =
1  1 1 R λ Li2+ 2 ∞  4
=νH =R H 12  2 − 2  = H .......(1)
λH 2 ∞  4

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 11

Step 3: Finding the ratio of the series limit

Dividing equation (1) by equation (2), we get Hence, the ratio of the series limits for wave
RH number of the Balmer series of hydrogen and
νH 1 1
4 Li2+ is
= = 9
νLi2+ 9R H 9
4 Option (d) is the correct answer.

Finding the transition

Which of the following transitions corresponds to the fourth line of the Balmer series?
(a) 6 and 2 (b) 5 and 2 (c) 4 and 1 (d) 5 and 1

Solution

For Balmer series, n1 = 2 and n2 > 2

First line of the Balmer series found when the electron transit 3 → 2
Second line of the Balmer series found when the electron transit 4 → 2
Third line of the Balmer series found when the electron transit 5 → 2
Fourth line of the Balmer series found when the electron transit 6 → 2
Hence, option (a) is the correct answer.

Finding the number of the shell

The wavenumber of a spectral line in the emission spectrum of hydrogen will be equal to 8/9
times the Rydberg constant if the electron jumps from which among the following options?
(a) n = 3 to n = 1 (b) n = 9 to n = 1 (c) n = 10 to n = 1 (d) n = 2 to n = 1

Solution

The wavelength corresponding to the emission 8 R  1 1 

spectrum is = H
R H 12  2 − 2 
9  n1 n2 
1 8 RH
=ν=
λ 9  1 1 2  1 1 
R H  2 −=  R 1  − 
Using the Rydberg formula, 1 3 
2 H
 n1
2
n 22 
1  1 1
= ν= RH Z 2  2 − 2  Comparing, we get n1 = 1 and n2 = 3
λ n
 1 n2 
Hence, for n = 3 to n = 1, the wavenumber
Substituting the value of atomic number of of the spectral line is equal to 8/9 times the
Hydrogen, Z = 1 Rydberg constant.
 1 1  Option (a) is the correct answer.
=ν R H 12  2 − 2 
 n1 n2 

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 12

Finding the ratio of frequency

What is the ratio of the frequency corresponding to the third line of the Lyman series of a hydrogen
spectrum to that of the first line of the Balmer series of a Li2+ spectrum?
(a) 5 : 4 (b) 4 : 5 (c) 4 : 3 (d) 3 : 4

Solution

Step 1: Calculating the frequency of the third line in the Lyman series
Using the Rydberg formula The third line in Lyman series corresponds to
 1 n2 = 4 to n1 = 1
1 1
= ν= RH Z 2  2 − 2  And for the hydrogen atom, atomic number
λ  n1 n2 
Z=1
Also, we know,
ν1  1 1
c 1 ν = R H 12  2 − 2 
ν= ⇒ = c 1 4 
λ λ c
Where c is the speed of light and ν is the ν 1 15 R H
=
frequency c 16
Substituting the value of the wavelength in terms 15R × c
ν1 = H .......(1)
of the frequency 16
ν  1 1 
= R H Z2  2 − 2 
c  n1 n2 

Step 2: Calculating the frequency of the first Step 3: Finding the ratio of frequency
line of the Balmer series Dividing equation (1) by equation (2) to get the
Using the formula ratio of frequency
ν  1 1 15 R H × c
= RH Z 2  2 − 2  ν1
c  n1 n2  16
=
ν2 5 RH × c
The first line of the Balmer series corresponds 4
to n1 = 2 and n2 = 3
15
Atomic number (Z) of Li2+ = 3
ν 1 16
=
ν2  1 1 ν2 5
= R H 32  2 − 2 
c 2 3  4
ν 2 5R H ν1 3
= =
c 4 ν2 4
5R × c Hence, option (d) is the correct answer.
ν2 = H .......(2)
4

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 13

Finding the transition of same wavelength

What transition in the hydrogen spectrum would have the same wavelength as the Balmer
transition n = 4 to n = 2 in the He+ spectrum?
(a) n = 3 to n = 1 (b) n = 3 to n = 2 (c) n = 4 to n = 1 (d) n = 2 to n = 1

Solution

Step 1: Calculating the wavelength of the Balmer series in He+

Using the Rydberg formula 1  1 1
= R H 22  2 − 2 
1  1 1  λ He+ 2 4 
= ν = R H Z2  2 − 2 
λ  n1 n2 
1  1 1
= R H  2
− 2 
Atomic number of He+ (Z) = 2, n1 = 2 and n2 = 4 λ He+ 1 2 
Substituting the values in the formula,

Step 2: Calculating the wavelength of H Step 3: Calculating the transition in the

Using the Rydberg formula hydrogen spectrum
According to the question, the hydrogen
1  1 1 
= ν = R H Z2  2 − 2  spectrum would have the same wavelength as
λ  n1 n2  the Balmer transition n = 4 to n = 2 in the He+
spectrum.
Atomic number of the hydrogen atom (Z) = 1
λ H =λ He+
1  1 1 
= R H 12  2 − 2  1 1
λH  n1 n2  =
λ H λ He+
1  1 1 
= RH  2 − 2   1 1   1 1
λH  n1 n2  RH  2 − 2  = RH  2 − 2 
 n1 n2  1 2 
Comparing both the sides, we get,
n1 = 1 and n2 = 2
Hence, option (d) is the correct answer.

Summary Sheet

• The study of spectra is known as spectroscopy. An instrument that is used to separate the
radiations of different wavelengths is known as spectrograph or spectroscope.
• Spectrum obtained after passing radiations through the spectroscope is known as spectrogram.
• Based on origin spectrum can be classified as
■ Emission spectrum ■  Absorption spectrum

• Emission spectrum is the spectrum of radiation emitted by a substance.

• There are two types of emission spectrum on the basis of nature.
■ Continuous spectrum ■  Discrete spectrum

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 14

• Continuous spectrum is the continuous distribution of colours (VIBGYOR) such that each colour
merges into the next one.
• Discontinuous or discrete spectra consist of only some wavelengths of light, unlike the spectra
of white light.
• Discrete spectrum can be subdivided into the following:
■ Line spectrum ■  Band spectrum

• Line spectrum: It is an ordered arrangement of the lines of a particular wavelength separated

by a dark space.
• When the continuous band is separated by a dark space, it is known as the band spectrum.
• When a continuous spectrum of electromagnetic radiation is passed through a sample (solution
or gas), certain wavelengths are absorbed by the sample that are used to excite the electrons
to higher energy levels. When we obtain the spectrum of the remaining radiation, we observe
dark lines corresponding to the wavelengths that are missing from the spectrum. This is known
as absorption spectrum.
• The wavelength of the hydrogen spectrum is classified in a series that is known as the spectral
series.
• During the de-excitation of electrons from higher energy levels to lower energy levels, electrons
can take many pathways. On the basis of the final state to which the electrons de-excite, the line
spectra are divided into following series:

Series n1 n2 Main spectral lines

Lyman 1 2, 3, 4, 5, 6,...∞ ultraviolet

Balmer 2 3, 4, 5, 6, 7,...∞ visible + ultraviolet

Paschen 3 4, 5, 6, 7, 8,...∞ infrared

Brackett 4 5, 6, 7, 8, 9,...∞ infrared

Pfund 5 6, 7, 8, 9, 10,...∞ infrared

Humphrey 6 7, 8, 9, 10,…...∞ far infrared

• Rydberg formula
1  1 1
= RH Z 2  2 − 2 
λ  n1 n2 

This can also be written as
912
λ= Å
 1 1
Z2  2 − 2 
 n1 n2 
Where
RH = Rydberg’s constant
RH = 1.09678 × 107 m-1 ≅ 1.1 × 107 m-1
Value of n will be an integer and n1 < n2

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